JPH04325417A - Manufacture of bi series oxide superconductor - Google Patents
Manufacture of bi series oxide superconductorInfo
- Publication number
- JPH04325417A JPH04325417A JP3124995A JP12499591A JPH04325417A JP H04325417 A JPH04325417 A JP H04325417A JP 3124995 A JP3124995 A JP 3124995A JP 12499591 A JP12499591 A JP 12499591A JP H04325417 A JPH04325417 A JP H04325417A
- Authority
- JP
- Japan
- Prior art keywords
- phase
- oxide superconductor
- low
- based oxide
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000002887 superconductor Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 16
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 7
- 229910052745 lead Inorganic materials 0.000 claims abstract description 5
- 238000005336 cracking Methods 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract 2
- 230000001105 regulatory effect Effects 0.000 abstract 2
- 239000012071 phase Substances 0.000 description 56
- 239000010408 film Substances 0.000 description 26
- 239000000843 powder Substances 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000000758 substrate Substances 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 229910052712 strontium Inorganic materials 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical group CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 2
- 159000000021 acetate salts Chemical class 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 238000007606 doctor blade method Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- VJMAITQRABEEKP-UHFFFAOYSA-N [6-(phenylmethoxymethyl)-1,4-dioxan-2-yl]methyl acetate Chemical class O1C(COC(=O)C)COCC1COCC1=CC=CC=C1 VJMAITQRABEEKP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Compositions Of Oxide Ceramics (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明はＢｉ系酸化物超電導体の
製造方法に関するものであって、超電導転移温度（Ｔｃ
）が１１０Ｋ程度を示す高Ｔｃ相の生成率が高いＢｉ系
酸化物超電導体の製造方法に関するものである。[Field of Industrial Application] The present invention relates to a method for producing a Bi-based oxide superconductor, and relates to a method for producing a Bi-based oxide superconductor, and relates to a superconducting transition temperature (Tc
The present invention relates to a method for manufacturing a Bi-based oxide superconductor that has a high production rate of a high Tc phase with a temperature of about 110K.
【０００２】0002
【従来の技術】Ｂｉ系酸化物超電導体には、超電導転移
温度（Ｔｃ）が８０Ｋ程度である低Ｔｃ相と１１０Ｋ程
度である高Ｔｃ相が存在し、Ｂｉ，Ｓｒ，Ｃａ，Ｃｕの
モル比がほぼ２：２：１：２の場合には低Ｔｃ相となり
、およそ２：２：２：３の場合（但しＢｉの一部がＰｂ
により置換されている）には高Ｔｃ相となることが知ら
れている。この様に高Ｔｃ相Ｂｉ系酸化物超電導体は、
低Ｔｃ相Ｂｉ系酸化物超電導体に比べてＣａとＣｕのモ
ル比が高く、且つＰｂを含んでいるものである。[Prior Art] Bi-based oxide superconductors have a low Tc phase with a superconducting transition temperature (Tc) of about 80K and a high Tc phase with a superconducting transition temperature (Tc) of about 110K, and the molar ratio of Bi, Sr, Ca, and Cu is When the ratio is approximately 2:2:1:2, it becomes a low Tc phase, and when it is approximately 2:2:2:3 (however, some of the Bi is Pb
) is known to result in a high Tc phase. In this way, the high Tc phase Bi-based oxide superconductor is
It has a higher molar ratio of Ca and Cu than the low Tc phase Bi-based oxide superconductor, and also contains Pb.
【０００３】ところで酸化物超電導体粉末の製造方法と
しては、固相法や共沈法及びゾル・ゲル法等の湿式法が
あり、例えば固相法を用いて高Ｔｃ相を主体とするＢｉ
系酸化物超電導体を得ようとする場合、Ｂｉ，Ｐｂ，Ｓ
ｒ，Ｃａ及びＣｕの酸化物または炭酸塩を用いてこれら
を上記高Ｔｃ相の金属組成比になる様に混合し、８００
℃付近で仮焼と粉砕を繰り返して高Ｔｃ相成分が多い粉
末を得ることが一般的である。尚上記粉末を用いて成形
体を得るにあたっては、金型成形、ＣＩＰ成形、ＨＩＰ
成形またはキャスティング法などにより、８００〜８７
０℃で焼成し所望の形に成形すればよい。By the way, methods for producing oxide superconductor powder include wet methods such as solid phase method, coprecipitation method, and sol-gel method.
When trying to obtain a system oxide superconductor, Bi, Pb, S
Using oxides or carbonates of r, Ca, and Cu, these were mixed so as to have the metal composition ratio of the above high Tc phase, and 800
It is common to repeat calcination and pulverization at around 0.degree. C. to obtain a powder containing a large amount of high Tc phase components. In order to obtain a molded body using the above powder, molding, CIP molding, HIP
800-87 by molding or casting method etc.
It may be fired at 0°C and molded into a desired shape.
【０００４】また高Ｔｃ相酸化物超電導体の厚膜を製造
する方法としては、スプレー法とドクターブレード法が
あり、前者の方法は高Ｔｃ相の金属組成比に近い各金属
元素の硝酸塩や有機酸塩の溶液を、セラミックス製や金
属製等の基板上にスプレーし、６００〜８００℃の仮焼
と、８００〜８７０℃の本焼とからなる熱処理を行ない
、超電導の膜を形成するものである。但し本方法は膜厚
に応じてスプレー、仮焼及び本焼からなる一連の工程を
何度も繰り返す必要があり、厚膜の製作には適していな
い。[0004] Methods for producing thick films of high Tc phase oxide superconductors include the spray method and the doctor blade method. The former method uses nitrates and organic A superconducting film is formed by spraying an acid salt solution onto a substrate made of ceramics, metal, etc., and performing heat treatment consisting of calcination at 600 to 800°C and final firing at 800 to 870°C. be. However, this method requires repeating a series of steps consisting of spraying, calcination, and final firing many times depending on the film thickness, and is not suitable for producing thick films.
【０００５】一方後者の方法は、前述の方法等で得られ
た酸化物超電導体粉末をスラリー化した後、ドクターブ
レードを用いて銀等の金属基板上に塗膜し、乾燥・焼成
して厚膜を形成する方法である。On the other hand, in the latter method, the oxide superconductor powder obtained by the above-mentioned method is made into a slurry, and then coated on a metal substrate such as silver using a doctor blade, dried and fired to form a thick film. This is a method of forming a film.
【０００６】しかしながら上記のいずれの方法で高Ｔｃ
相のＢｉ系酸化物超電導体を得ようとしても、例えば８
４０℃で６０時間焼成しても高Ｔｃ相は３０％程度しか
得られず、生成率が低いと共に生成速度が遅いので高Ｔ
ｃ相Ｂｉ系酸化物超電導体の生産性に優れた製造方法が
要望されている。However, in any of the above methods, high Tc
Even if you try to obtain a Bi-based oxide superconductor with a phase of 8
Even after firing at 40°C for 60 hours, only about 30% of the high Tc phase is obtained.
There is a need for a manufacturing method with excellent productivity for c-phase Bi-based oxide superconductors.
【０００７】さらに厚膜を形成しようとする場合にあっ
ては、膜厚を大きくしようとすると割れが発生するとい
う問題を有している。Furthermore, when attempting to form a thick film, there is a problem in that cracks occur when the film thickness is increased.
【０００８】[0008]
【発明が解決しようとする課題】本発明は上記事情に着
目してなされたものであって、高Ｔｃ相の生成率が高く
、且つ生成速度も速くて生産性に優れ、しかも膜厚とし
た際に割れの発生が少ないＢｉ系酸化物超電導体の製造
方法を提供しようとするものである。[Problems to be Solved by the Invention] The present invention has been made in view of the above-mentioned circumstances, and it is an object of the present invention to provide a high-Tc phase that has a high production rate and a high production rate, resulting in excellent productivity and a thin film. It is an object of the present invention to provide a method for manufacturing a Bi-based oxide superconductor in which cracks are less likely to occur.
【０００９】[0009]
【課題を解決するための手段】上記目的を達成した本発
明とは、（Ｂｉ，Ｐｂ）：Ｓｒ：Ｃａ：Ｃｕの金属組成
比が２：２：２：３である高Ｔｃ相を主相とするＢｉ系
酸化物超電導体の製造方法であって、上記金属組成比が
２：２：１：２である低Ｔｃ相のＢｉ系酸化物超電導体
に、Ｃａ化合物，Ｃｕ化合物及びＰｂ化合物を含有する
溶液またはゾルを加えて熱処理を行い、低Ｔｃ相を高Ｔ
ｃ相に転化させることを要旨とするものである。[Means for Solving the Problems] The present invention, which achieves the above object, consists of a high Tc phase having a metal composition ratio of (Bi, Pb):Sr:Ca:Cu of 2:2:2:3. A method for producing a Bi-based oxide superconductor, which comprises adding a Ca compound, a Cu compound, and a Pb compound to a low-Tc phase Bi-based oxide superconductor having a metal composition ratio of 2:2:1:2. The low Tc phase is converted into a high Tc phase by adding the containing solution or sol and performing heat treatment.
The gist of this is to convert it into c-phase.
【００１０】0010
【作用】Ｂｉ系酸化物超電導体の高Ｔｃ相は低Ｔｃ相を
経て生成すると考えられ、本発明者は低Ｔｃ相を用いて
これを高Ｔｃ相化する方法を研究し本発明に想到した。[Operation] It is thought that the high Tc phase of a Bi-based oxide superconductor is generated through the low Tc phase, and the present inventors researched a method of converting this into a high Tc phase using the low Tc phase, and came up with the present invention. .
【００１１】本発明方法により高Ｔｃ相を主相とする成
形体または膜を作製しようとする場合、Ｃａ化合物，Ｃ
ｕ化合物及びＰｂ化合物を含有する溶液またはゾルを用
い、主として低Ｔｃ相のＢｉ系酸化物超電導体からなる
成形体または膜上にディッピング法またはスプレー法等
により超電導の前駆体膜を形成した後、熱処理を施せば
よい。[0011] When attempting to produce a molded body or film having a high Tc phase as a main phase by the method of the present invention, Ca compounds, C
After forming a superconducting precursor film on a molded body or film mainly consisting of a low Tc phase Bi-based oxide superconductor by dipping or spraying using a solution or sol containing a u compound and a Pb compound, Heat treatment may be performed.
【００１２】本発明方法により高Ｔｃ相を主相とする膜
を作製しようとする場合、Ｃａ化合物，Ｃｕ化合物及び
Ｐｂ化合物を含有する溶液またはゾルと、主として低Ｔ
ｃ相のＢｉ系酸化物超電導体からなる粉末とを混合し、
これをスクリーン印刷法等により基板上に塗布した後、
熱処理を施せばよい。[0012] When attempting to produce a film having a high Tc phase as the main phase by the method of the present invention, a solution or sol containing a Ca compound, a Cu compound, and a Pb compound and a mainly low Tc phase are used.
Mixing with powder consisting of a c-phase Bi-based oxide superconductor,
After applying this onto the substrate by screen printing method etc.
Heat treatment may be performed.
【００１３】本発明方法により高Ｔｃ相を主相とする基
板を作製しようとする場合、Ｃａ化合物，Ｃｕ化合物及
びＰｂ化合物を含有する溶液またはゾルと、主として低
Ｔｃ相のＢｉ系酸化物超電導体からなる粉末とを混合し
たスラリー液を用いて、キャスティングによりシート状
に成形し、これに熱処理を施せばよく、上記スラリー液
には増粘剤，結合剤や可塑剤等を加えて調整してもよい
。When a substrate having a high Tc phase as the main phase is to be produced by the method of the present invention, a solution or sol containing a Ca compound, a Cu compound, and a Pb compound and a Bi-based oxide superconductor mainly having a low Tc phase are used. It is sufficient to use a slurry liquid mixed with a powder consisting of a powder, form it into a sheet by casting, and heat-treat it. The slurry liquid may be adjusted by adding a thickener, a binder, a plasticizer, etc. Good too.
【００１４】本発明方法により高Ｔｃ相を主相とする粉
末を作製しようとする場合、Ｃａ化合物，Ｃｕ化合物及
びＰｂ化合物を含有する溶液またはゾルと、主として低
Ｔｃ相のＢｉ系酸化物超電導体からなる粉末とを混合し
、乾燥または仮焼して上記粉末粒子の周りに、Ｃａ化合
物，Ｃｕ化合物及びＰｂ化合物が均一に分散した層を形
成し、これに熱処理を施せばよい。When a powder having a high Tc phase as the main phase is to be produced by the method of the present invention, a solution or sol containing a Ca compound, a Cu compound, and a Pb compound and a Bi-based oxide superconductor mainly having a low Tc phase are used. A layer in which a Ca compound, a Cu compound, and a Pb compound are uniformly dispersed is formed around the powder particles by drying or calcining the powder, and then heat-treating the layer.
【００１５】上記の様に本発明に係る方法においては、
低Ｔｃ相のＢｉ系酸化物超電導体とＣａ化合物，Ｃｕ化
合物及びＰｂ化合物を含有する液相とが反応する為、低
Ｔｃ相の有する配向性が利用でき、ａ軸及びｂ軸のサイ
ズはほぼそのままでｃ軸の配向を向上させることによっ
て高Ｔｃ相のＢｉ系酸化物超電導体を得ることができる
。As described above, in the method according to the present invention,
Since the Bi-based oxide superconductor in the low Tc phase reacts with the liquid phase containing Ca compounds, Cu compounds, and Pb compounds, the orientation of the low Tc phase can be utilized, and the sizes of the a-axis and b-axis are approximately the same. A Bi-based oxide superconductor with a high Tc phase can be obtained by improving the c-axis orientation as it is.
【００１６】また低Ｔｃ相Ｂｉ系酸化物超電導体は比較
的生成しやすいので、該低Ｔｃ相Ｂｉ酸化物超電導体を
からなる粉末，成形体及び膜等を利用すれば高Ｔｃ相Ｂ
ｉ系酸化物超電導体を製造するのに必要な長い焼成時間
が短縮できる。Furthermore, since low Tc phase Bi-based oxide superconductors are relatively easy to produce, high Tc phase B
The long firing time required to produce i-based oxide superconductors can be shortened.
【００１７】さらにドクターブレード法を用いて厚膜を
形成する場合、処理溶液やゾルに低Ｔｃ相の粉末を混ぜ
ることによって塗布剤中の固形分濃度が増し、熱処理時
における膜の収縮を少なくできるために、乾燥速度を上
げることが可能であり、しかも割れの発生が抑制できる
。また固形分濃度を上げることによって塗布１回当りの
膜厚を厚くすることができ、厚膜の作製には有利である
。Furthermore, when forming a thick film using the doctor blade method, by mixing a low Tc phase powder into the processing solution or sol, the solid content concentration in the coating agent can be increased and shrinkage of the film during heat treatment can be reduced. Therefore, it is possible to increase the drying speed and also suppress the occurrence of cracks. Furthermore, by increasing the solid content concentration, the film thickness per coating can be increased, which is advantageous for producing thick films.
【００１８】[0018]
実施例１
市販品の低Ｔｃ相粉末を自動乳鉢で粉砕して、平均粒径
を３μｍとした。Ｐｂ，Ｃａ，Ｃｕの酢酸塩をそれぞれ
２．５ ×１０−２ｍｏｌ ずつ秤量し、酢酸水に溶解
させた後、加熱濃縮して粘調なゾル液とした。得られた
ゾル液に、最終組成が高Ｔｃ相の組成になるように上記
低Ｔｃ相粉末を加え、加温しながら均一に混合して粘度
約８００ｃｐｓ のペーストとした。該ペーストを用い
てＡｇ基板上にスクリーン印刷法（＃２５０メッシュ）
で膜を形成した。上記ペーストの一回当りの塗布厚みは
約１μｍとし、３００℃乾燥、８００℃仮焼を繰り返し
て約１０μｍの仮焼膜を形成した。尚３００℃乾燥後、
直ちに８００℃で仮焼しても割れは発生しなかった。Example 1 A commercially available low Tc phase powder was ground in an automatic mortar to have an average particle size of 3 μm. Acetate salts of Pb, Ca, and Cu were each weighed in an amount of 2.5 x 10-2 mol, dissolved in aqueous acetic acid, and then heated and concentrated to obtain a viscous sol solution. The low Tc phase powder was added to the obtained sol solution so that the final composition would be a high Tc phase composition, and the powder was uniformly mixed while heating to form a paste with a viscosity of about 800 cps. Screen printing method (#250 mesh) on an Ag substrate using the paste
A film was formed. The thickness of each application of the above paste was about 1 μm, and drying at 300° C. and calcining at 800° C. were repeated to form a calcined film of about 10 μm. After drying at 300℃,
No cracking occurred even after immediate calcining at 800°C.
【００１９】上記仮焼膜を８４０℃で６０時間焼成する
ことにより、高Ｔｃ相が既に約４５％に達した超電導膜
が得られ、Ｔｃを測定したところＴｃｏｎｓｅｔは１０
５Ｋ、Ｔｃｏｆｆｓｅｔは８５Ｋであった。By baking the above calcined film at 840° C. for 60 hours, a superconducting film in which the high Tc phase already reached about 45% was obtained, and when Tc was measured, Tconset was 10
5K, Tcoffset was 85K.
【００２０】比較例１
Ｂｉ，Ｓｒ，Ｃａ，Ｃｕの各酢酸塩を高Ｔｃ相の金属組
成比に配合し、Ｂｉの一部（１２．５％）はＰｂの酢酸
塩で置換した。これらの出発原料を酢酸水に溶解させた
後、加熱濃縮してディップコーティングに適した約１０
０ｃｐｓ の粘度に調節した。尚上記ディップコーティ
ングにおいて一回当りの膜厚が約１μｍ以上になると熱
処理中に割れが多発した。従って割れを押えるために一
回当りの塗布厚みを約８０００Åとし、２００℃乾燥、
５００℃仮焼、８００℃仮焼を１０回繰り返して最終約
８μｍの仮焼膜を形成した。Comparative Example 1 Acetate salts of Bi, Sr, Ca, and Cu were added to the metal composition ratio of the high Tc phase, and a portion of Bi (12.5%) was replaced with acetate of Pb. After dissolving these starting materials in aqueous acetic acid, the mixture is heated and concentrated to give a solution of about 100 ml, which is suitable for dip coating.
The viscosity was adjusted to 0 cps. In the dip coating described above, when the film thickness per coating was about 1 μm or more, many cracks occurred during the heat treatment. Therefore, in order to prevent cracking, the coating thickness per coat was approximately 8000 Å, dried at 200°C,
Calcining at 500° C. and 800° C. was repeated 10 times to form a final calcined film with a thickness of about 8 μm.
【００２１】仮焼膜を８４０℃で６０時間焼成したが、
高Ｔｃ相の生成率は約１０％であり、実施例１で得られ
た超電導膜に比べて劣っていた。またこの膜のＴｃｏｎ
ｓｅｔは１０５Ｋであったが、Ｔｃｏｆｆｓｅｔは５０
Ｋと低かった。[0021] The calcined film was fired at 840°C for 60 hours, but
The generation rate of the high Tc phase was about 10%, which was inferior to the superconducting film obtained in Example 1. Also, the Tcon of this film
set was 105K, but Tcoffset was 50
It was as low as K.
【００２２】実施例２
実施例１と同様にして作製した低Ｔｃ相の粉末とゾルと
の混合物に、アルコールに溶解させたＰＶＡを１％加え
よく混合してスラリー液とした。該スラリー液を離型紙
の上にキャスティングし、一昼夜室温にて乾燥したのち
、８０℃で乾燥させて離型した。得られたグリーンシー
トから３ｃｍ×３ｃｍ×０．３μｍの成形体を切り取り
、さらに２００℃で乾燥させ、５００℃で仮焼後８４０
℃で６０時間焼成してセラミックス基板とした。Example 2 To a mixture of low Tc phase powder and sol prepared in the same manner as in Example 1, 1% of PVA dissolved in alcohol was added and thoroughly mixed to obtain a slurry liquid. The slurry liquid was cast onto release paper, dried at room temperature for a day and night, and then dried at 80° C. and released from the mold. A 3 cm x 3 cm x 0.3 μm molded body was cut from the obtained green sheet, further dried at 200°C, and after calcined at 500°C, it was heated to 840°C.
It was fired at ℃ for 60 hours to obtain a ceramic substrate.
【００２３】Ｘ線回折法で同定したところ高Ｔｃ相は約
４０％に達しており、Ｃ軸の配向性も優れていた。また
この超電導セラミックス基板のＴｃを測定したところＴ
ｃｏｎｓｅｔは１０５Ｋ、Ｔｃｏｆｆｓｅｔは８０Ｋで
あった。Identification by X-ray diffraction revealed that the high Tc phase accounted for approximately 40%, and the C-axis orientation was excellent. Also, when Tc of this superconducting ceramic substrate was measured, T
Conset was 105K and Tcoffset was 80K.
【００２４】比較例２
Ｂｉ，Ｓｒ，Ｃａ，Ｃｕの各酢酸塩を高Ｔｃ相の金属組
成比に配合し、Ｂｉの一部（１２．５％）はＰｂの酢酸
塩で置換した。これらの出発原料を酢酸水に溶解させた
後、加熱濃縮して約４００ｃｐｓ の粘度とし、水に溶
解させたＰＶＡを１％加えてキャスティング可能なゾル
とした。
このゾルを用いて、実施例２と同様に離型紙の上にキャ
スティングし、離型、切断後、２００℃で乾燥させた。
しかしながら多くの割れが発生し基板の形で焼成するこ
とはできなかった。Comparative Example 2 Acetate salts of Bi, Sr, Ca, and Cu were added to the metal composition ratio of the high Tc phase, and a portion of Bi (12.5%) was replaced with acetate of Pb. These starting materials were dissolved in aqueous acetic acid, heated and concentrated to a viscosity of about 400 cps, and 1% of PVA dissolved in water was added to form a castable sol. Using this sol, it was cast onto release paper in the same manner as in Example 2, released, cut, and dried at 200°C. However, many cracks occurred and it was not possible to sinter it in the form of a substrate.
【００２５】そこで、２００℃乾燥後、粉末状に粉砕し
、８４０℃での焼成時間と高Ｔｃ相の生成量との関係に
ついて、実施例１のペーストを乾燥の後同条件で焼成し
たものと比較した。結果は図１に示す。明らかに、低Ｔ
ｃ相を混合させたペーストを用いた方が高Ｔｃ相の生成
速度が速いことが分かる。Therefore, after drying at 200°C, the paste was pulverized into powder, and the relationship between the firing time at 840°C and the amount of high Tc phase produced was compared with that of the paste of Example 1, which was dried and then fired under the same conditions. compared. The results are shown in Figure 1. Obviously, low T
It can be seen that the rate of generation of the high Tc phase is faster when the paste containing the c phase is used.
【００２６】[0026]
【発明の効果】本発明は以上の様に構成されているので
、高Ｔｃ相の生成率が高く、且つ生成速度も速くて生産
性に優れ、しかも厚膜や成形体とした際に割れの発生が
少ないＢｉ系酸化物超電導体の製造方法が提供できるこ
ととなった。[Effects of the Invention] Since the present invention is constructed as described above, the production rate of the high Tc phase is high, the production speed is also fast, and the productivity is excellent. Moreover, when it is made into a thick film or a molded product, it is possible to prevent cracking. It is now possible to provide a method for producing a Bi-based oxide superconductor that generates little generation.
【図１】本発明に係るＢｉ系酸化物超電導体及び比較例
における高Ｔｃ相の生成速度を示すグラフである。FIG. 1 is a graph showing the formation rate of a high Tc phase in a Bi-based oxide superconductor according to the present invention and a comparative example.
Claims (1)
金属組成比が２：２：２：３である高Ｔｃ相を主相とす
るＢｉ系酸化物超電導体の製造方法であって、上記金属
組成比が２：２：１：２である低Ｔｃ相のＢｉ系酸化物
超電導体に、Ｃａ化合物，Ｃｕ化合物及びＰｂ化合物を
含有する溶液またはゾルを加えて熱処理を行い、低Ｔｃ
相を高Ｔｃ相に転化させることを特徴とするＢｉ系酸化
物超電導体の製造方法。1. A method for producing a Bi-based oxide superconductor having a high Tc phase as a main phase in which the metal composition ratio of (Bi, Pb):Sr:Ca:Cu is 2:2:2:3, , a solution or sol containing a Ca compound, a Cu compound, and a Pb compound is added to the low Tc phase Bi-based oxide superconductor having a metal composition ratio of 2:2:1:2, and heat treatment is performed to obtain a low Tc phase.
A method for producing a Bi-based oxide superconductor, the method comprising converting a phase into a high Tc phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3124995A JPH04325417A (en) | 1991-04-26 | 1991-04-26 | Manufacture of bi series oxide superconductor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3124995A JPH04325417A (en) | 1991-04-26 | 1991-04-26 | Manufacture of bi series oxide superconductor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04325417A true JPH04325417A (en) | 1992-11-13 |
Family
ID=14899291
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3124995A Withdrawn JPH04325417A (en) | 1991-04-26 | 1991-04-26 | Manufacture of bi series oxide superconductor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04325417A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993022799A1 (en) * | 1992-04-27 | 1993-11-11 | Unisearch Limited | Silver clad superconductor composite |
-
1991
- 1991-04-26 JP JP3124995A patent/JPH04325417A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1993022799A1 (en) * | 1992-04-27 | 1993-11-11 | Unisearch Limited | Silver clad superconductor composite |
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